Refining of petroleum distillates



April 21, 1942.l B. G. GlLLEsPlE 2,280,227

REFI'NING 0F PETROLEUM DISTILLATES Filed Slep't. 8, 1939` LIGHT fri/vf cur" HEA yfPR/ME cuT Patented Apr.` `2l, 1942 fulal'rleo4 ,Lerares ATENT 'f "OFFICE I REFININGOF PErRoLEUMDIsTILLA'rEs I Bruce Cranford, yJ.,as`signr` to 'I I lStandard Ol Development Company," a corb pOr'ation'ol D aware I "The present invention relates to the production il; Conditions are maintained in rerundistillaof high `quality petroleum distillates. WrIheiinvention unit I4t'o remove overheadsubstantially-the tion is particularly directed to the production of entire quantityof thenaphtha bymeans of line stability secured `by distilling` said distilla'tes in petroleum distillates ofimproved color and 'color I8. A relativelysmall amountiof naphtha and `the aromatic amine are removed from distillation the' presence of a relatively highboiling aromatic' unit l 4 by means of line I9 and treatedin a man# i f l i ner to regenerate the `high boiling aromatic amine." t..

It is known in the art to' reflnepe'troleumoils amine.

by distilling the sameand then to contact the ``The process of my invention may be Widely resulting distillates in various ways withclaya lo varied. Although any aromatic amine havinga metallic exidea bauxite and the iilieiniorderto b'oilins point above about `425 F. may be eniremoveY color bodies fromthe same and tostabi'- ployed,` as for example, benzyl anillne, alphalizelthe distillates against subsequent decomposior betanaphthylanne, aminodiphenyl, Xylidine, tion evidenced by additional coloribo'dies' formi toluidine, diphenylethylenediamine, ornaphing.' These distillates I are usually treated by la thylaniline. I have found that particularly. desirpassing thesame through bedsofc'layor by conable results are secured when 'olistlling` a tacting the distillate with sulfuric acidlo with petroleumoil; in the presence of naphtlylamines', an equivalent acid; These methodaj although `llaltllllly alphanaphthylamine. Thealmati satisfactory for the removal of color bodies, have amine should be in liquid phase under they disthe disadvantage inthat aconsiderablelosslis tillaton conditions. general, it is preferable experienced when removing `theonlorbodies in `that the aromatic amine have a boiling point at this manner. I` havenow discovered a processv 1 ?a`St100f Ff, preferably at least 200 F- abOVe the for the removal of color bodies and for the pro- Engler distillation :end `point 0f the StOCk being duction of colorstabilized oil which will not sub-` distilled The quantity 0f alOmtC amine 6mstantially alect the yield of the color improved D10Yed-Will-deDel1d llDOnthe particular amine and color stabilized product. In accordance with Ilti1iZd,t1lQ boiling range 0f the Oil being'treated,

my invention, petroleum 011s are distilled in `the 'as wellias upon the color characteristicsrof the cil'. presence of a high boiling aromatic amine, In general, the amount of'the aromaticamine `'I'heprocess of my invention may be readily emDlOyed ShOllld be ill the'lalgeabve 1%;p1efunderstood by reference to the attached drawing 30 erably ill the range 0f abOllt 25% t0 3%, and illustrating one modication of the same. A ShOllld IlOt eXCSed alOOllt 5%- The diStillatOn petroleum cil which `for the purpose of the de` operation likewise may be conducted under varscription is taken to be a petroleum crude oil is ous temperature and pressureconditions. I have introduced into still I by means of feed line `2. i found that. in general, it is desirable to remove I Conditions are `maintained on still I to remove 3u overhead at least 90% of the distillate, preferaoverhead fixed gas by means of line 3 and to .segbly about 95% of the distillate. Especially desirregate a light prime cut, a heavy prime out, a able results are secured by utilizing less than 3% gas oil cut, and a bottoms cut which are removed of the aromatic aminek and conducting the disby means of line 4, 5, 6, and l respectively. The tillation operation to remove overhead at least gas oil cut is then subjected to temperature and lo 98% of the petlOlelllIl diStllate- The remaining pressure conditions in cracking unit 8 tc convert 2% of the petroleum distillate and 3% 0f the the gas oil out boiling in the range from about aromatic amine is then removed as a bottoms. 400 F. to 700 F. into petroleum oil fractions By conducting this rerllllllillg diStillatiOIl Operaboiling in the range below about 400 F. This tion in the manner described, 2% to 5% higher so-called cracked naphtha fraction is removed TLD yields are obtained for a iinal product of equivfrcm cracking unit 8 by means of line 9 and inalent quality.

. troduced into debutanization 'and stabilization Ill Order t0 illustrate the iIlVentiOIl, the followunit I0. Fixed gas fractions are removed from ing examples are given which should not be condebutanization and stabilization unit I0 by strued as limiting the same in any manner whati means of line II andthe stabilized naphtha boil- 5U soever: ing below about 400 F. by means of line I2. The EXAMPLE 1 heavy ends are removedifrcm unit I 0 by means A heavy naphtha (produced by a catalytic of Ime '3 and may be handled m any manner cracking operation) and boiling in therange desirable. The cracked distillate may be comy from about 225 E to 400 F, had a +13 Saybolt bined with thevirgin fractions and then passed U" colors. Operations were Conducted 'in which to return distillation unit I4 by means of line I I5. Prior to introducing saidiproduc'ts into re- I *0010? determined by A- S T. M. test D156-38.

run unit I4, a small quantity of an aromatic portions of this distillate were rerun in the abamine is introduced into line I5 by means of line l K sence ci an aromatic amine and in the presence I6 and the mixture passed through mixing unit UU of a mixture of alphanaphthylamine and benzylanaline. The results of these operations were as follows:

Table 1 Color Saybolt Naphtha before rerunning 13 Naphtha rerun in absence of aromatic amine Naphtha rerun in presence of 3% of aromatic amine mixture consisting of equal quantities of alphanaphthylamine and benzylanaline EXAMPLE 2 amine 16 Naphtha rerun in presence of 5% alphanaphthylamine 28 TheL naphthas distilled in the manner described above were subjected to a colorhold test byheating for 16 hours at a temperature of 212 F. The results of these tests were as follows:

Table 3 Color after Color after colorhold distillation test Naphtha. distilled in absence of aromatic amine.

Naphtha distilled in presence of 5% alphanaphthylamine.

16 Straw colored (too low to read on Saybolt Chmometer) The process of the present invention is not to be limited by any theory or mode of operation, but only in and by the following claims.

I claim:

1. Process for the rening of petroleum distillates for the production of products of improved color and color stability comprising nishing said distillates by distilling the same in the presence of about 1% to 5% of a naphthylamine under conditions to remove overhead at least 90% of the distillate and to remove as a bottoms undistilled oil containing the naphthylamine.

2. Process in accordance with claim 1 in which the naphthylamine is alphanaphthylamine.

3. Process for the production of petroleum oils boiling in the range below about 400 F. having improved color and color stability, said oils being secured from cracking processes, comprising distilling said oils in the presence of about 2% to 3% of a naphthylamine under conditions to remove overhead oil fractions boiling in the gasoline boiling range and removing as a bottoms the undistilled fractions and the naphthylamine.

4. A process for refining petroleum distillates boiling in the range below about 400 F. and having improved color and color stability which comprises adding to the petroleum distillate about 1% to 5% of a heat stable aromatic amine having a boiling point at least 100 F. and up to 200 F. higher than the end boiling point of the petroleum distillate to be treated, distilling the petroleum distillate to remove overhead about 98% of the treated distillate and to remove as bottoms undistilled petroleum oil containing the aromatic amine, the aromatic amine being in the liquid phase during the distillation.

BRUCE G. GILLESPIE. 

